CN109608579A - A kind of preparation method of the polymer of cross-linked structure - Google Patents
A kind of preparation method of the polymer of cross-linked structure Download PDFInfo
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- CN109608579A CN109608579A CN201811407297.8A CN201811407297A CN109608579A CN 109608579 A CN109608579 A CN 109608579A CN 201811407297 A CN201811407297 A CN 201811407297A CN 109608579 A CN109608579 A CN 109608579A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention discloses a kind of preparation method of the polymer of cross-linked structure and applications.The polymer is using tapioca as primary raw material, sweet potato starch is 24 hours dry in the vacuum oven at 60 DEG C, using dimethyl diallyl ammonium chloride as cation graft monomer, ethyl acrylate and the chloro- 2- hydroxypropyl methacrylate of 3- are anionic grafting monomer, N; N " methylene-bisacrylamide is internal crosslinker, sodium polyphosphate is outside cross-linking agent, obtains adsorptivity double cross connection both sexes tapioca through the processing steps such as cationization, anionic grafting, inside and outside double cross connection, washing by soaking, drying, crushing in aqueous solvent.Double cross, which joins both sexes adsorptivity tapioca, has superior absorption property.It simultaneously as chelating effect can occur with metal positive and negative ion for anions and canons group in double cross connection both sexes adsorptivity tapioca, and can be released in isoelectric point, separation of metal ions can be recycled using this property.Double cross prepared by the present invention connection both sexes adsorptivity tapioca can Reusability, this will play a positive role to the improvement of heavy metal pollution.
Description
Technical field
The present invention relates to a kind of preparation methods of the polymer of cross-linked structure.
Background technique
Crosslinking amphoteric starch be using the reactivity of hydroxyl in starch glucose unit, by its respectively with anions and canons
Etherifying agent or amphoteric ion, crosslinking agent are reacted and are obtained.Adsorptivity crosslinking amphoteric starch refers on starch glucose chain link simultaneously
Insoluble starch derivative containing positive and negative two kinds of charge groups, with only contain a kind of charge insoluble anion or sun from
Sub- starch is compared, its performance is more unique.Compared with the polyelectrolyte with, this quasi polymer shows very in salting liquid
Apparent anti-polyelectrolyte solution behavior.The crosslinking amphoteric starch derivative of environmental sensitivity is in environment such as temperature, pH value, electric field
Deng reversible contraction and swelling can occur when changing, artificial intelligence material is made into for the controlled release of drug, inductor, people
Work muscle etc..Crosslinking amphoteric starch is but also widely used for separation and concentration heavy metal and rare metal etc..The absorption of high-crosslinking-degree
Property amphoteric starch derivative is more unique for the absorption property of metal ion, this will play actively the improvement of heavy metal pollution
Effect.Since crosslink density is low, high-water expansion, hydrone easily infiltrates into the adsorptivity amphoteric starch derivative of low crosslinking degree
Macromolecule network is expanded in starch derivatives, becomes high water absorption state.
It is for fibre mostly by natural polymer grafted propylene acetoacetic ester, then by the method that basic hydrolysis is anion
Dimension element prepares carboxyethyl cellulose etc..It is existing it is some report such as starch is crosslinked with ethylene oxide, then with chloroacetic acid with
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride carries out the crosslinking amphoteric starch that anions and canonsization reaction is prepared for single cross connection respectively.But
The deficiencies of that there are the degrees of cross linking is low, absorption property is limited.Therefore the synthesis and property of research double cross connection both sexes adsorptivity starch derivatives
Can exploitation, be a Xiang Xinying and significant work.
Summary of the invention
The purpose of the invention is to improve the absorption property of starch derivatives, shortens the production cycle, a kind of crosslinking is provided
The preparation method of the polymer of reticular structure.
Specific steps are as follows:
(1) tapioca is 24 hours dry in the vacuum oven at 60 DEG C.
(2) butt tapioca obtained by step (1) and deionized water being added in reactor and being made into mass fraction is 30%
~35% starch suspension.
(3) it will be equivalent to the dimethyl diallyl chlorination that the mass fraction of 1~3 times of butt tapioca quality is 60%
Ammonium cation monomer is added in suspension obtained by step (2)；Being warming up to temperature of reaction system is 40~50 DEG C, anti-under stirring
Answer 1~1.5 hour, used in reaction process mass fraction for 10%~20% sodium hydroxide solution control system pH 9~
12。
(4) analysis pure acrylic acid ethyl ester, the pure 3- of analysis that will be equivalent to 0.5~1 times of butt tapioca quality respectively are chloro-
2- hydroxypropyl methacrylate is added in glass container and is mixed evenly, and adds and is equivalent to butt tapioca quality
3% N, N'- methylene-bisacrylamide, stir evenly to obtain monomer mixed solution at room temperature.
(5) weigh respectively be equivalent to step (4) ethyl acrylate mass fraction be 0.2%~0.5% ammonium persulfate and
Sodium hydrogensulfite is that 1:1 is dissolved in deionized water by ammonium persulfate and sodium hydrogensulfite mass ratio, stirs evenly be made at room temperature
The initiator solution that mass fraction is 10%.
(6) step (3) resulting material is heated to 60~70 DEG C, drops evenly monomer mixed solution obtained by step (4), and same
Step drops evenly the initiator solution that the mass fraction of step (5) preparation is 10%, is added dropwise in 4~5 hours；Then exist
Stirring is lower, and the reaction was continued 20~30 minutes, then system temperature is cooled to 40 DEG C.
(7) it weighs and is equivalent to 1%~5% sodium polyphosphate of butt tapioca quality and is added to obtained by step (6)
In material, the copper bromide for being equivalent to butt tapioca quality 0.1%~0.3% is added, carries out cross-linking reaction 0.5 at 40 DEG C
~1 hour.
(8) it weighs and is equivalent to the sodium hydrate solid that step (4) ethyl acrylate the mass ratio of the material is 1:1 and is dissolved in and quantitatively going
It is made into the sodium hydroxide solution that mass fraction is 10%~15% in ionized water, then solution constant pressure funnel is controlled
It is added drop-wise in 1.5~2 hours in feed liquid obtained by step (7), then proceedes to reaction 1 hour.
(9) pH to 5~6.5 for HCl solution regulating step (8) the gained system for being 10% with mass fraction；
(10) being put into step (9) resulting material and being equivalent to the volume fraction of 4~7 times of butt tapioca quality is 80%
Ethanol solution in impregnate 24 hours to remove the impurity such as unreacted monomer, homopolymerization and copolymer.
(11) with the dehydrated alcohol for being equivalent to 3~4 times of butt tapioca quality that the deionized water in step (10) is de-
It goes.
(12) step (11) products therefrom is placed in 80 DEG C of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is crushed, sieving obtains white granular product.
(14) product graft rate is measured using mass method.The calculation formula of grafting rate is as follows:
G=(W1/W0) × 100%
In formula: G --- grafting rate, %；
The quality of W1 --- graft copolymer, unit g；
The quality of W0 --- tapioca, unit g.
(15) measurement of the degree of cross linking: according to the principle that settlement volume is smaller, the degree of cross linking is bigger, i.e., cross-linked amylum derivative is heavy
Drop product and degree of cross linking negative correlation；The present invention characterizes the degree of cross linking using settlement volume indirectly.Specific assay method is as follows: matching
The converted starch suspension that mass fraction processed is 2%, constant temperature stirring, heat preservation 2 minutes, take out cooling in 82 DEG C~85 DEG C water-baths
To room temperature.Taking two volumes is the tool plug graduated centrifuge tube of 10mL, is separately added into gelatinized corn starch liquid 10mL.With 4000 revs/min
Centrifuge is centrifuged 2 minutes, then pours into supernatant in the tool plug graduated centrifuge tube of same volume, reading ml, and it is heavy to calculate
Drop product.Same sample measures 3 times, is averaged.Calculation formula is as follows:
Settlement volume=10-V
In formula: V --- supernatant volume, Unit/mL.
Polymer obtained by a kind of preparation method of the polymer of cross-linked structure is in the improvement of heavy metal pollution
Application.
Double cross, which joins both sexes adsorptivity tapioca, has superior absorption property.Simultaneously as double cross joins both sexes adsorptivity
Chelating effect can occur with metal positive and negative ion for anions and canons group in tapioca, and can be discharged in isoelectric point
Out, separation of metal ions can be recycled using this property.Double cross connection both sexes adsorptivity tapioca prepared by the present invention can be anti-
Multiple to use, this will play a positive role to the improvement of heavy metal pollution.
Specific embodiment
Embodiment 1:
(2) it takes butt tapioca obtained by 24g step (1) to be added in 500mL four-hole boiling flask with 56mL deionized water to be made into
The starch suspension that mass fraction is 30%.
(3) 30g mass fraction is added to step (2) institute for 60% dimethyl diallyl ammonium chloride cationic monomer
It obtains in 30% starch suspension；Being warming up to temperature of reaction system is 40 DEG C, stirs lower reaction 1 hour, uses matter in reaction process
The sodium hydroxide solution control system pH that score is 10% is measured 10.
(4) 15g is analyzed into pure acrylic acid ethyl ester respectively, 15g analyzes the chloro- 2- hydroxypropyl methacrylate of pure 3- and glass is added
Be mixed evenly in glass container, add 0.72g N, N'- methylene-bisacrylamide, stir evenly at room temperature monomer is mixed
Close liquid.
(5) 0.5g ammonium persulfate and 0.5g sodium hydrogensulfite are weighed respectively, are dissolved in 9mL deionized water, are stirred at room temperature
Uniformly it is made into the initiator solution that mass fraction is 10%.
(6) step (3) resulting material is heated to 70 DEG C, drops evenly monomer mixed solution obtained by step (4), and synchronized
The initiator solution that the mass fraction that even a dropping step (5) is prepared is 10%, is added dropwise in 4 hours；Then under stiring after
Continuous reaction 30 minutes, then system temperature is cooled to 40 DEG C.
(7) it weighs 0.5g sodium polyphosphate to be added in step (6) resulting material, adds 0.24g copper bromide, at 40 DEG C
It carries out cross-linking reaction 0.5 hour.
(8) weigh 6g sodium hydrate solid be dissolved in be made into 54mL deionized water mass fraction be 10% sodium hydroxide it is molten
Liquid, then the solution constant pressure funnel is controlled and was added drop-wise in feed liquid obtained by step (7) at 1.5 hours, then proceed to reaction 1
Hour.
(9) pH to 6.5 for HCl solution regulating step (8) the gained system for being 10% with mass fraction.
(10) by step (9) resulting material be put into 120g volume fraction be 80% ethanol solution in impregnate 24 hours with
Remove the impurity such as unreacted monomer, homopolymerization and copolymer.
(11) deionized water in step (10) is sloughed with 95g dehydrated alcohol.
(12) step (11) products therefrom is placed in 80 DEG C of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is crushed, sieving obtains white granular product.
It (14) is 120% with mass method measurement grafting rate, settlement volume 0.25mL.
Embodiment 2:
(2) it takes butt tapioca obtained by 26g step (1) to be added in 500mL four-hole boiling flask with 54mL deionized water to be made into
The starch suspension that mass fraction is 32.5%.
(3) 40g mass fraction is added to step (2) institute for 60% dimethyl diallyl ammonium chloride cationic monomer
It obtains in 32.5% starch suspension；Being warming up to temperature of reaction system is 45 DEG C, stirs lower reaction 1.5 hours, adopts in reaction process
The sodium hydroxide solution control system pH for being 10% with mass fraction is 11.
(4) 20g is analyzed into pure acrylic acid ethyl ester respectively, 20g analyzes the chloro- 2- hydroxypropyl methacrylate of pure 3- and glass is added
Be mixed evenly in glass container, add 0.78g N, N'- methylene-bisacrylamide, stir evenly at room temperature monomer is mixed
Close liquid.
(5) 0.8g ammonium persulfate and 0.8g sodium hydrogensulfite are weighed respectively, are dissolved in 14.4mL deionized water, are stirred at room temperature
It mixes and is uniformly made into the initiator solution that mass fraction is 10%.
(6) step (3) resulting material is heated to 60 DEG C, drops evenly monomer mixed solution obtained by step (4), and synchronized
The initiator solution that the mass fraction that even a dropping step (5) is prepared is 10%, is added dropwise in 4.5 hours；Then under stiring
The reaction was continued 30 minutes, then system temperature is cooled to 40 DEG C.
(7) it weighs 1.0g sodium polyphosphate to be added in step (6) resulting material, adds 0.35g copper bromide, at 40 DEG C
It carries out cross-linking reaction 0.5 hour.
(8) weigh 8g sodium hydrate solid be dissolved in be made into 52mL deionized water mass fraction be 13.33% hydroxide
Sodium solution, then the solution constant pressure funnel is controlled and was added drop-wise in feed liquid obtained by step (7) at 2 hours, it then proceedes to anti-
It answers 1 hour.
(9) pH to 6.5 for HCl solution regulating step (8) the gained system for being 10% with mass fraction；
(10) by step (9) resulting material be put into 150g volume fraction be 80% ethanol solution in impregnate 24 hours with
Remove the impurity such as unreacted monomer, homopolymerization and copolymer.
(11) deionized water in step (10) is sloughed with 120g dehydrated alcohol.
(12) step (11) products therefrom is placed in 80 DEG C of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is crushed, sieving obtains white granular product.
It (14) is 215% with mass method measurement grafting rate, settlement volume 0.19mL.
Product is analyzed through IR, and 3382.79cm-1 obviously broadens, this is N, C-H vibration of N'- methylene-bisacrylamide
Absorption peak；1658.23cm-1 is N, the C=O vibration absorption peak of N'- methylene-bisacrylamide；1580.34cm-1 being propionic acid
Base-COO-vibration absorption peak；1424.85cm-1 is N, C-N vibration absorption peak of N'- methylene-bisacrylamide；
1209.94cm-1 is C-N vibration absorption peak of dimethyl diallyl ammonium chloride；1157.36cm-1~1018.30cm-1 is bright
Aobvious to broaden, this is P=O, the vibration absorption peak of P-O.
Particle surface pattern through sem analysis, after comparison before modified, it can be seen that the granule-morphology of log sweet potato starch is circle
Shape is approximate circle, and particle is more complete, and surface is more smooth；Double cross joins both sexes adsorptivity tapioca polymeric particles tight adhesion
And rough surface, there are apparent damaged rill and cave, destroys the structure of log sweet potato starch, structure occurs obvious
Variation, this may be to destroy crystal region under grafting and alkalinity effect, thus further illustrate starch conversion success.
Claims (2)
1. a kind of preparation method of the polymer of cross-linked structure, which is characterized in that specific steps are as follows:
(1) tapioca is 24 hours dry in the vacuum oven at 60 DEG C；
(2) butt tapioca and deionized water obtained by step (1) are added in reactor be made into mass fraction be 30%~
35% starch suspension；
(3) the dimethyl diallyl ammonium chloride sun that the mass fraction that will be equivalent to 1~3 times of butt tapioca quality is 60%
Ion monomer is added in suspension obtained by step (2)；Being warming up to temperature of reaction system is 40~50 DEG C, stir lower reaction 1~
1.5 hours, it was 10%~20% sodium hydroxide solution control system pH 9~12 that mass fraction is used in reaction process；
(4) the analysis pure acrylic acid ethyl ester, the pure chloro- 2- hydroxyl of 3- of analysis of 0.5~1 times of butt tapioca quality be will be equivalent to respectively
Propyl methacrylate is added in glass container and is mixed evenly, and adds and is equivalent to butt tapioca quality 3%
N, N'- methylene-bisacrylamide stir evenly to obtain monomer mixed solution at room temperature；
(5) it weighs respectively and is equivalent to ammonium persulfate and sulfurous that step (4) ethyl acrylate mass fraction is 0.2%~0.5%
Sour hydrogen sodium is that 1:1 is dissolved in deionized water by ammonium persulfate and sodium hydrogensulfite mass ratio, stirs evenly be made into quality at room temperature
The initiator solution that score is 10%；
(6) step (3) resulting material is heated to 60~70 DEG C, drops evenly monomer mixed solution obtained by step (4), and synchronized
The initiator solution that the mass fraction that even a dropping step (5) is prepared is 10%, is added dropwise in 4~5 hours；Then under stiring
The reaction was continued 20~30 minutes, then system temperature is cooled to 40 DEG C；
(7) it weighs and is equivalent to 1%~5% sodium polyphosphate of butt tapioca quality and is added to step (6) resulting material
In, the copper bromide for being equivalent to butt tapioca quality 0.1%~0.3% is added, carries out cross-linking reaction 0.5~1 at 40 DEG C
Hour；
(8) weigh be equivalent to step (4) ethyl acrylate the mass ratio of the material be 1:1 sodium hydrate solid be dissolved in quantitative deionization
It is made into the sodium hydroxide solution that mass fraction is 10%~15% in water, then solution constant pressure funnel is controlled 1.5
It is added drop-wise in~2 hours in feed liquid obtained by step (7), then proceedes to reaction 1 hour；
(9) pH to 5~6.5 for HCl solution regulating step (8) the gained system for being 10% with mass fraction；
(10) step (9) resulting material is put into the second for being equivalent to that the volume fraction of 4~7 times of butt tapioca quality is 80%
Alcohol solution for soaking 24 hours to remove the impurity such as unreacted monomer, homopolymerization and copolymer；
(11) deionized water in step (10) is sloughed with the dehydrated alcohol for being equivalent to 3~4 times of butt tapioca quality；
(12) step (11) products therefrom is placed in 80 DEG C of baking ovens and is dried to constant weight；
(13) step (12) products therefrom is crushed, sieving obtains white granular product.
2. polymer obtained by a kind of preparation method of the polymer of cross-linked structure according to claim 1 is in weight
Application in the improvement of metallic pollution.
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| CN201811407297.8A CN109608579A (en) | 2018-11-23 | 2018-11-23 | A kind of preparation method of the polymer of cross-linked structure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357744A (en) * | 2019-08-13 | 2019-10-22 | 山东胜伟盐碱地科技有限公司 | Soil conditioner and preparation based on coal-fired flue gas desulfurization gypsum, application method |
-
2018
- 2018-11-23 CN CN201811407297.8A patent/CN109608579A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357744A (en) * | 2019-08-13 | 2019-10-22 | 山东胜伟盐碱地科技有限公司 | Soil conditioner and preparation based on coal-fired flue gas desulfurization gypsum, application method |
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